EP2684851A2 - Verre de silice synthétique pour des moules de Nanoimprint et procédé de fabrication du verre par hydrolyse à la flamme - Google Patents

Verre de silice synthétique pour des moules de Nanoimprint et procédé de fabrication du verre par hydrolyse à la flamme Download PDF

Info

Publication number
EP2684851A2
EP2684851A2 EP13175453.3A EP13175453A EP2684851A2 EP 2684851 A2 EP2684851 A2 EP 2684851A2 EP 13175453 A EP13175453 A EP 13175453A EP 2684851 A2 EP2684851 A2 EP 2684851A2
Authority
EP
European Patent Office
Prior art keywords
quartz glass
synthetic quartz
hours
temperature
glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13175453.3A
Other languages
German (de)
English (en)
Other versions
EP2684851B1 (fr
EP2684851A3 (fr
Inventor
Shigeru Maida
Hisatoshi Otsuka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Publication of EP2684851A2 publication Critical patent/EP2684851A2/fr
Publication of EP2684851A3 publication Critical patent/EP2684851A3/fr
Application granted granted Critical
Publication of EP2684851B1 publication Critical patent/EP2684851B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
    • C03B19/1453—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/225—Refining
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/07—Impurity concentration specified
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
    • C03B2201/21—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with molecular hydrogen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
    • C03B2201/23—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/20—Doped silica-based glasses containing non-metals other than boron or halide
    • C03C2201/21—Doped silica-based glasses containing non-metals other than boron or halide containing molecular hydrogen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/20—Doped silica-based glasses containing non-metals other than boron or halide
    • C03C2201/23—Doped silica-based glasses containing non-metals other than boron or halide containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/40—Gas-phase processes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/50—After-treatment
    • C03C2203/52—Heat-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • This invention relates to nanoimprint mold-forming synthetic quartz glass having a high gas permeability and a method of preparing the same.
  • the lithography process for manufacturing semiconductor devices uses a light source of shorter wavelength.
  • the photolithography using ArF excimer laser (193 nm) is the mainstream.
  • a future transition of photolithography to extreme ultraviolet (EUV) is regarded promising to gain a higher integration density.
  • EUV extreme ultraviolet
  • the nanoimprint technology is also in the limelight for the fabrication of semiconductor devices having a half pitch of 32 nm or less.
  • the nanoimprint technology is expected to find diversified applications of fabricating optical waveguides, biochips, and optical storage media.
  • a mold also referred to as stamper or template
  • the mold is pressed to a resin material or resist layer coated on a substrate to transfer the fine pattern to the resin layer.
  • the mold is pressed to a resist layer coated on a semiconductor wafer, typically silicon wafer to transfer the fine pattern to the resist layer.
  • the mold In the step of pressing the mold to a resist layer on a recipient substrate to transfer the fine pattern to the resist layer, the mold must be pressed such that even fine recesses of the pattern over its entire extent may be filled with the resin material. If the resin material is incompletely spread, with air bubbles left, the fine pattern on the mold is not completely transferred.
  • the transfer step is generally carried out in a least viscous gas atmosphere, for example, a helium-containing atmosphere so that no bubbles are left behind.
  • the step of pressing the mold to a resin material is slowed down, residual bubbles may be minimized or eliminated.
  • the slow step is one of barriers against the application of the nanoimprint technology to semiconductor fabrication because the semiconductor fabrication process requires to increase the throughput, that is, the number of processed units in a given time.
  • the nanoimprint mold is generally made of synthetic quartz glass having excellent light transmittance, thermal stability, mechanical properties and working properties, the glass has a low helium gas permeability and thus makes only a little contribution to throughput improvement.
  • WO 2011/096368 discloses a mold made of TiO 2 -SiO 2 glass having a high helium gas permeability.
  • the TiO 2 -SiO 2 glass has the advantage that its light transmittance and thermal stability are equivalent or superior to synthetic quartz glass.
  • the TiO 2 -SiO 2 glass has problems including a negative impact on the fine pattern of irregularities of the mold due to striae and a high manufacture cost.
  • An object of the invention is to provide synthetic quartz glass having a high helium gas permeability and suited for the nanoimprint technology and a method for preparing the same.
  • a synthetic quartz glass having a hydroxyl group concentration of at least 300 ppm and a Raman peak attributable to hydrogen molecule equal to or less than the detection limit has a high helium gas permeability and is suited for forming nanoimprint molds.
  • the invention provides a method for preparing a synthetic quartz glass for forming nanoimprint molds, comprising the steps of subjecting a silicon-providing feedstock to flame hydrolysis in an oxyhydrogen flame to produce fine particles of silica, depositing the silica fine particles on a rotating quartz glass target while concurrently melting and vitrifying them, thereby forming a synthetic quartz glass ingot, shaping, annealing, and effecting dehydrogenation treatment by holding at a temperature of at least 600°C and a pressure of up to 5 Pa for a time of at least 12 hours.
  • the shaping step includes hot shaping at 1,500 to 1,800°C for 1 to 10 hours, and the annealing step includes holding at a temperature of 1,050 to 1,300°C for at least 5 hours and slowly cooling at a rate of up to 20°C/hr to a temperature of 800 to 1,000°C.
  • the invention provides a synthetic quartz glass for forming nanoimprint molds, having an OH group concentration of at least 300 ppm and a Raman peak attributable to hydrogen molecule equal to or less than the detection limit.
  • the synthetic quartz glass has a birefringence of up to 8 nm/cm, a birefringence distribution of up to 5 nm/cm, a fictive temperature of up to 910°C, and/or a fictive temperature distribution of up to 10°C.
  • the invention provides a synthetic quartz glass for forming nanoimprint molds, which is prepared by the method of the invention and has an OH group concentration of at least 300 ppm and a Raman peak attributable to hydrogen molecule equal to or less than the detection limit.
  • nanoimprint mold made of the synthetic quartz glass defined above.
  • the synthetic quartz glass of the invention has a high helium gas permeability and is suited for forming nanoimprint molds.
  • the method for preparing synthetic quartz glass for forming nanoimprint molds preferably follows the so-called direct process, specifically including the steps of feeding a combustible gas containing hydrogen gas and a combustion-supporting gas containing oxygen gas to a burner in a quartz glass manufacturing furnace and effecting combustion to form an oxyhydrogen flame at the burner tip, feeding a silicon-providing feedstock into the flame to subject the feedstock to oxidation or flame hydrolysis to produce fine particles of silica or silicon oxide, depositing the silica fine particles on a target disposed forward of the burner tip, and concurrently melting and vitrifying them into transparent glass, thereby forming a synthetic quartz glass ingot.
  • FIG. 1 there is illustrated an exemplary apparatus for producing a synthetic quartz glass ingot.
  • a target 2 of quartz glass is mounted on a rotating support 1.
  • a feedstock evaporator 3 is charged with a silicon-providing feedstock 4.
  • An inert gas 5 such as argon is introduced into the feedstock 4 to carry the vapor of the silicon-providing feedstock 4 on the inert gas 5 (carrier).
  • a quartz glass burner 7 includes a central nozzle which receives a gas mixture of the feedstock vapor 4 on carrier gas 5 with oxygen gas 6.
  • the burner 7 also includes tubes surrounding the central nozzle, which receive oxygen gas 8, hydrogen gas 9, hydrogen gas 10, and oxygen gas 11, in the order from inside to outside.
  • the silicon-providing feedstock gas 4 and oxyhydrogen flame 12 are injected from the burner 7 toward the target 2.
  • Silica fine particles 13 are deposited on the target 2 while they are concurrently melted and vitrified, yielding a synthetic quartz glass ingot 14.
  • the resulting ingot is hot shaped into a predetermined shape and annealed, yielding synthetic quartz glass for forming nanoimprint molds as will be described later.
  • Another method may be employed for the preparation of a synthetic quartz glass ingot.
  • the other method includes the steps of feeding a combustible gas containing hydrogen gas and a combustion-supporting gas containing oxygen gas to a burner in a quartz glass manufacturing furnace and effecting combustion to form an oxyhydrogen flame, feeding a silicon-providing feedstock into the flame to produce fine particles of silica, spraying and depositing the silica fine particles on a rotating heat resistant substrate of quartz, axially withdrawing the substrate at a constant rate, thereby forming a porous silica sintered body, and heating the body in a water vapor atmosphere containing an inert gas for vitrification, thereby forming a synthetic quartz glass ingot.
  • quartz glass manufacturing furnace used herein may be either vertical or horizontal.
  • the silicon-providing feedstock used herein may comprise any well-known organosilicon compounds. Examples include chlorinated silane compounds such as silicon tetrachloride, dimethyldichlorosilane, and methyltrichlorosilane; and alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane.
  • chlorinated silane compounds such as silicon tetrachloride, dimethyldichlorosilane, and methyltrichlorosilane
  • alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane.
  • the combustible gas used herein is a hydrogen-containing gas, typically hydrogen gas, optionally in combination with another gas such as carbon monoxide, methane and propane.
  • the combustion-supporting gas used herein is an oxygen-containing gas, typically oxygen gas.
  • the synthetic quartz glass ingot thus prepared is hot shaped into a predetermined shape, preferably at a temperature of 1,500 to 1,800°C, more preferably 1,600 to 1,750°C for 1 to 10 hours.
  • the quartz glass ingot as hot shaped is annealed such that it may have a birefringence, birefringence distribution, fictive temperature and fictive temperature distribution in the desired ranges.
  • Effective means for letting birefringence and birefringence distribution fall in the desired ranges is by holding in air or an inert gas atmosphere such as nitrogen at an anneal temperature of 1,050 to 1,300°C for a time of preferably at least 5 hours, more preferably at least 10 hours, and even more preferably at least 15 hours, and slowly cooling down to a near-strain-point temperature of 800 to 1,000°C at a rate of preferably up to 20°C/hr, more preferably up to 10°C/hr, and even more preferably up to 5°C/hr.
  • Effective means for letting fictive temperature and fictive temperature distribution fall in the desired ranges is by slowly cooling from 1,025°C to 860°C at a rate of preferably up to 3°C/hr, more preferably up to 2°C/hr, and even more preferably up to 1°C/hr, and optionally, but more effectively holding at 860°C for at least 10 hours.
  • the synthetic quartz glass as annealed is preferably heat treated so as to reduce the hydrogen molecule concentration to or below the detection limit.
  • the heat treatment temperature is at least 600°C, preferably at least 700°C.
  • the upper limit of heat treatment temperature is preferably up to 1,000°C, more preferably up to 900°C, and even preferably up to 850°C.
  • the holding time is at least 12 hours, preferably at least 25 hours, more preferably at least 50 hours, and even more preferably at least 75 hours.
  • the pressure is up to 5 Pa, preferably up to 2.5 Pa, and more preferably up to 1 Pa.
  • the synthetic quartz glass After the synthetic quartz glass is heat treated under reduced pressure, it is processed into a predetermined size by cutting, slicing, grinding or otherwise machining, and polished on a double-side polishing machine using a polishing slurry of silicon oxide, aluminum oxide, molybdenum oxide, silicon carbide, diamond, cerium oxide or colloidal silica, and further machined to produce a nanoimprint member.
  • the synthetic quartz glass of the invention is used as molds for the nanoimprint technology.
  • the synthetic quartz glass should have a hydroxyl group concentration of at least 300 ppm, preferably at least 400 ppm. If the OH group concentration is less than 300 ppm, then synthetic quartz glass has a low helium gas permeability. Although the relationship of OH group concentration to helium gas permeability is not definitely recognized, it is believed that OH groups act in favor of pores in synthetic quartz glass through which helium gas permeates. It is also believed effective for providing affinity to resist that the glass contains OH groups in a concentration of at least 300 ppm. The upper limit of OH group concentration is up to 1,500 ppm, though not critical.
  • FTIR Fourier transform infrared spectrophotometry
  • the synthetic quartz glass when analyzed by Raman spectroscopy, should have a peak attributable to hydrogen molecule equal to or less than the detection limit, that is, a hydrogen molecule concentration of up to 8.5 ⁇ 10 15 molecules/cm 3 .
  • Raman spectroscopy analysis is carried out under the following conditions.
  • the hydrogen molecule concentration is measured by spectrophotometry as described in Zhurnal Priklandnoi Spektroskopii, Vol. 46, No. 6, 987-991 (June 1987 ). Specifically, the hydrogen molecule concentration in quartz glass is determined from a ratio of the intensity of hydrogen molecule at wavenumber 4135 cm -1 for hydrogen molecules in quartz glass to the intensity of Raman band at wavenumber 800 cm -1 for SiO 2 .
  • the glass is preferably heat treated under reduced pressure.
  • the heat treatment temperature is at least 600°C, preferably at least 700°C.
  • the upper limit of heat treatment temperature is preferably up to 1,000°C, more preferably up to 900°C, and even preferably up to 850°C.
  • the holding time is at least 12 hours, preferably at least 25 hours, more preferably at least 50 hours, and even more preferably at least 75 hours.
  • the upper limit of holding time is preferably up to 300 hours for economy, though not critical.
  • the pressure is up to 5 Pa, preferably up to 2.5 Pa, and more preferably up to 1 Pa.
  • the lower limit of pressure is preferably at least 0.01 Pa, though not critical.
  • the synthetic quartz glass should preferably have a birefringence of up to 8 nm/cm, more preferably up to 5 nm/cm, even more preferably up to 2 nm/cm, and most preferably up to 1 nm/cm.
  • the birefringence distribution is preferably up to 5 nm/cm, more preferably up to 3 nm/cm. If birefringence exceeds 8 nm/cm or if birefringence distribution exceeds 5 nm/cm, then a fine pattern to be formed on a nanoimprint mold made of synthetic quartz glass may be deformed.
  • the lower limits of birefringence and birefringence distribution are both preferably at least 0.01 nm/cm, though not critical.
  • the glass is annealed by holding in air or an inert gas atmosphere such as nitrogen at an anneal temperature of 1,050 to 1,300°C for a time of preferably at least 5 hours, more preferably at least 10 hours, and even more preferably at least 15 hours, and slowly cooling down to a near-strain-point temperature of 800 to 1,000°C at a rate of preferably up to 20°C/hr, more preferably up to 10°C/hr, and even more preferably up to 5°C/hr.
  • an inert gas atmosphere such as nitrogen
  • This annealing schedule is effective for suppressing the birefringence and birefringence distribution in a shaped synthetic quartz glass block.
  • the annealing at an adjusted cooling rate from the maximum temperature to the near-strain-point temperature is preferably followed by slow cooling from the near-strain-point temperature to a temperature in the range of 100 to 300°C at a rate of up to 40°C/hr, more preferably up to 20°C/hr, and even more preferably up to 10°C/hr.
  • Birefringence is determined by a birefringence meter, for example, ABR-10A by UNIOPT Corp. The maximum of the measurements at a multiplicity of spots is reported as birefringence, and a difference between maximum and minimum is reported as birefringence distribution.
  • the synthetic quartz glass should preferably have a fictive temperature of up to 910°C, more preferably up to 900°C, and even more preferably up to 890°C.
  • the fictive temperature is the maximum of fictive temperature measurements in quartz glass at a multiplicity of spots.
  • the fictive temperature distribution is preferably up to 10°C, more preferably up to 5°C.
  • the fictive temperature distribution is a difference between maximum and minimum among fictive temperature measurements in quartz glass at a multiplicity of spots. If fictive temperature exceeds 910°C or if fictive temperature distribution exceeds 10°C, then synthetic quartz glass may be less durable when used as nanoimprint molds.
  • the synthetic quartz glass has a fictive temperature of up to 910°C and a fictive temperature distribution of up to 10°C
  • the glass is preferably slowly cooled from 1,025°C to 860°C at a rate of up to 3°C/hr, more preferably up to 2°C/hr, and even more preferably up to 1°C/hr, and further preferably held at 860°C for at least 10 hours.
  • the fictive temperature is measured by the method described in J. Non-Cryst. Solids 185, 191 (1995 ).
  • the glass ingot was ground on its surface by an external cylindrical grinder to remove the unmelted silica or soot stuck to the ingot surface.
  • the ingot was immersed in a 50 wt% hydrofluoric acid solution for 3 hours, washed with deionized water, and dried in a clean booth.
  • the synthetic quartz glass ingot as surface-cleaned was placed in a high-purity carbon template having a high-purity carbon sheet set therein in an electric oven, and heated at a temperature of 1,780°C in an argon gas atmosphere for 40 minutes, whereby it was shaped into a synthetic quartz glass body of 160 mm ⁇ 160 mm ⁇ 210 mm long.
  • the shaped synthetic quartz glass body was sawed into a block of 50 mm thick.
  • the shaped synthetic quartz glass block as sawed had a hydrogen molecule concentration of 6 ⁇ 10 18 molecules/cm 3 at the center and 3 ⁇ 10 18 molecules/cm 3 at the periphery.
  • the shaped synthetic quartz glass block of 50 mm thick was placed in an atmospheric oven so that its surface of 160 mm ⁇ 160 mm might face the built-in heater.
  • the block was held at 1,145°C for 15 hours, slowly cooled down to 1,025°C at a rate of 5°C/hr, then slowly cooled down to 860°C at a rate of 1°C/hr, held at 860°C for 10 hours, and slowly cooled down to 150°C at a rate of 10°C/hr. Finally, with the power supply to the heater turned off, it was allowed to cool down.
  • the shaped synthetic quartz glass block as annealed was placed in a vacuum heating oven where it was held at 800°C and 0.8 Pa for 75 hours for dehydrogenation.
  • the shaped synthetic quartz glass block as dehydrogenated was sliced to a thickness of 6.8 mm and lapped. After the slice or substrate was lapped at its edge surfaces, it was roughly polished with a cerium oxide polishing slurry and then precision polished using an abrasive cloth of soft suede and a colloidal silica water dispersion having a SiO 2 concentration of 40 wt% as the polishing slurry. The polishing step was followed by cleaning and drying, yielding a polished substrate of 152.4 mm ⁇ 152.4 mm ⁇ 6.35 mm.
  • the polished substrate thus obtained was analyzed for OH group concentration, hydrogen molecule concentration, birefringence, and fictive temperature at a multiplicity of spots as shown in FIG. 2 .
  • Table 1 reports maximum, minimum and distribution value (Max - Min).
  • a polished silicon wafer was coated with a resist (MUR-XR01 by Maruzene Petrochemical Co., Ltd.) in a dotted pattern. At this point, only a central portion of the silicon wafer was not coated with the resist.
  • the polished synthetic quartz glass substrate was brought close to the silicon wafer from top and held to maintain a constant distance between the glass substrate and the silicon wafer. Bubbles having a diameter of about 100 ⁇ m were formed at the central portion of the silicon wafer and glass substrate where no resist was coated. A time passed until the bubbles extinguished was measured. The bubble extinction time is also shown in Table 1. It is noted that the gas permeability test was performed in a chamber filled with helium gas.
  • the shaped synthetic quartz glass block of 50 mm thick as annealed was placed in a vacuum heating oven where it was held at 600°C and 2.5 Pa for 12 hours to carry out dehydrogenation.
  • the process was the same as in Example 1 except the dehydrogenation vacuum heating step.
  • the results of measurement and gas permeability test are also shown in Table 1.
  • Example 1 The process was the same as in Example 1 except the ingot making step.
  • the results of measurement and gas permeability test are also shown in Table 1.
  • the shaped synthetic quartz glass block of 50 mm thick as annealed was placed in a vacuum heating oven where it was held at 400°C and 1.0 Pa for 25 hours to carry out dehydrogenation.
  • the process was the same as in Example 1 except the dehydrogenation vacuum heating step.
  • the results of measurement and gas permeability test are also shown in Table 1.
  • the porous silica sintered body was placed in a vacuum heating oven under a pressure below 0.3 Pa where it was heated from room temperature to 1,250°C at a rate of 10°C/hr, held at the temperature for 10 hours, and heated from 1,250°C to 1,500°C at a rate of 3°C/hr for transparent glass conversion, yielding a synthetic quartz glass body having a diameter of 140 mm and a length of 350 mm.
  • Example 1 The process was the same as in Example 1 except the ingot making step.
  • the results of measurement and gas permeability test are also shown in Table 1.
  • the porous silica sintered body was placed in an atmosphere of 95 vol% helium gas and 5 vol% water vapor where it was heated from room temperature to 1,250°C at a rate of 10°C/hr, held at the temperature for 10 hours, and heated from 1,250°C to 1,500°C at a rate of 3°C/hr for transparent glass conversion, yielding a synthetic quartz glass body having a diameter of 140 mm and a length of 350 mm.
  • Example 1 The process was the same as in Example 1 except the ingot making step.
  • the results of measurement and gas permeability test are also shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Glass Compositions (AREA)
  • Glass Melting And Manufacturing (AREA)
EP13175453.3A 2012-07-10 2013-07-08 Verre de silice sythétique pour des moules de nanoimprint et procédé de fabrication du verre par hydrolyse à la flamme Active EP2684851B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012154525 2012-07-10

Publications (3)

Publication Number Publication Date
EP2684851A2 true EP2684851A2 (fr) 2014-01-15
EP2684851A3 EP2684851A3 (fr) 2015-08-05
EP2684851B1 EP2684851B1 (fr) 2018-02-07

Family

ID=48747420

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13175453.3A Active EP2684851B1 (fr) 2012-07-10 2013-07-08 Verre de silice sythétique pour des moules de nanoimprint et procédé de fabrication du verre par hydrolyse à la flamme

Country Status (6)

Country Link
US (1) US9056785B2 (fr)
EP (1) EP2684851B1 (fr)
JP (1) JP5935765B2 (fr)
KR (1) KR101869989B1 (fr)
CN (1) CN103570225B (fr)
TW (1) TWI608997B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2910531A1 (fr) * 2014-02-21 2015-08-26 Shin-Etsu Chemical Co., Ltd. Procédé de traitement thermique de verre de quartz synthétique
US20220048811A1 (en) * 2019-05-07 2022-02-17 Ulvac Coating Corporation Quartz etching method and etched substrate

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2532508A4 (fr) * 2010-02-03 2014-01-08 Asahi Glass Co Ltd Procédé de fabrication d'article ayant sur sa surface une structure finement rugueuse
EP4015466A1 (fr) 2020-12-16 2022-06-22 Heraeus Quarzglas GmbH & Co. KG Procédé de fabrication de silice vitreuse synthétique
EP4015468A1 (fr) 2020-12-16 2022-06-22 Heraeus Quarzglas GmbH & Co. KG Procédé de fabrication de silice vitreuse synthétique

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011096368A1 (fr) 2010-02-03 2011-08-11 旭硝子株式会社 Procédé de fabrication d'article ayant sur sa surface une structure finement rugueuse

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3303918B2 (ja) * 1990-05-14 2002-07-22 東ソー・クォーツ株式会社 合成石英ガラス及びその製法
DE19841932A1 (de) * 1998-09-14 2000-03-16 Heraeus Quarzglas Optisches Bauteil aus Quarzglas und Verfahren für seine Herstellung
DE19850736C2 (de) * 1998-11-04 2003-04-17 Heraeus Tenevo Ag Kernglas für eine Vorform für eine optische Faser, unter Verwendung des Kernglases hergestellte Vorform, sowie Verfahren zur Herstellung des Kernglases einer Vorform für eine optische Faser
CN1226212C (zh) * 2001-04-19 2005-11-09 株式会社尼康 石英玻璃元件和投影曝光装置
DE10159961C2 (de) * 2001-12-06 2003-12-24 Heraeus Quarzglas Quarzglasrohling für ein optisches Bauteil sowie Verfahren zur Herstellung und Verwendung desselben
US7506522B2 (en) * 2004-12-29 2009-03-24 Corning Incorporated High refractive index homogeneity fused silica glass and method of making same
US7506521B2 (en) * 2004-12-29 2009-03-24 Corning Incorporated High transmission synthetic silica glass and method of making same
JP4487783B2 (ja) * 2005-01-25 2010-06-23 旭硝子株式会社 ＴｉＯ２を含有するシリカガラスの製造方法およびＴｉＯ２を含有するシリカガラスを用いたＥＵＶリソグラフィ用光学部材
US7928026B2 (en) * 2005-06-30 2011-04-19 Corning Incorporated Synthetic silica material with low fluence-dependent-transmission and method of making the same
JP4831328B2 (ja) * 2005-08-11 2011-12-07 信越化学工業株式会社 エキシマレーザ用合成石英ガラス基板の製造方法
EP1979279A1 (fr) * 2006-01-30 2008-10-15 Asahi Glass Co., Ltd. Verre de quartz synthétique à axes rapides de biréfringence répartis dans des directions tangentes à des cercles concentriques et procédé de production dudit verre
JP4925753B2 (ja) * 2006-07-11 2012-05-09 株式会社細川洋行 充填方法および包装体
US7592063B2 (en) * 2006-09-05 2009-09-22 Asahi Glass Company, Limited Quartz glass substrate and process for its production
JP5042714B2 (ja) * 2007-06-06 2012-10-03 信越化学工業株式会社 ナノインプリントモールド用チタニアドープ石英ガラス
JP2009013048A (ja) * 2007-06-06 2009-01-22 Shin Etsu Chem Co Ltd ナノインプリントモールド用チタニアドープ石英ガラス
JP5202141B2 (ja) * 2008-07-07 2013-06-05 信越化学工業株式会社 チタニアドープ石英ガラス部材及びその製造方法
US9067814B2 (en) * 2009-01-19 2015-06-30 Shin-Etsu Chemical Co., Ltd. Method of producing synthetic quartz glass for excimer laser
WO2011068100A1 (fr) * 2009-12-04 2011-06-09 旭硝子株式会社 Procédé de production d'un substrat en verre à base de silice pour un moule d'impression, et procédé de production d'un moule d'impression
JP5476982B2 (ja) * 2009-12-25 2014-04-23 信越化学工業株式会社 チタニアドープ石英ガラスの選定方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011096368A1 (fr) 2010-02-03 2011-08-11 旭硝子株式会社 Procédé de fabrication d'article ayant sur sa surface une structure finement rugueuse

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. NON-CRYST. SOLIDS, vol. 185, 1995, pages 191
ZHURNAL PRIKLANDNOI SPEKTROSKOPII, vol. 46, no. 6, June 1987 (1987-06-01), pages 987 - 991

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2910531A1 (fr) * 2014-02-21 2015-08-26 Shin-Etsu Chemical Co., Ltd. Procédé de traitement thermique de verre de quartz synthétique
US9487426B2 (en) 2014-02-21 2016-11-08 Shin-Etsu Chemical Co., Ltd. Heat treatment method of synthetic quartz glass
US20220048811A1 (en) * 2019-05-07 2022-02-17 Ulvac Coating Corporation Quartz etching method and etched substrate

Also Published As

Publication number Publication date
JP2014031308A (ja) 2014-02-20
CN103570225A (zh) 2014-02-12
TW201420522A (zh) 2014-06-01
JP5935765B2 (ja) 2016-06-15
EP2684851B1 (fr) 2018-02-07
TWI608997B (zh) 2017-12-21
CN103570225B (zh) 2018-11-23
KR101869989B1 (ko) 2018-06-22
EP2684851A3 (fr) 2015-08-05
US9056785B2 (en) 2015-06-16
US20140018229A1 (en) 2014-01-16
KR20140007761A (ko) 2014-01-20

Similar Documents

Publication Publication Date Title
EP1795506B2 (fr) Verre de silice dopée à l'oxyde de titane, méthode de fabrication, élément pour la lithographie aux rayons ultraviolets extrêmes et substrat pour photomasque
KR101869979B1 (ko) 티타니아 도핑 석영 유리 및 그의 제조 방법
EP2145865B1 (fr) Élément de verre de quartz dopé à l'oxyde de titane et procédé de fabrication
EP2511246B2 (fr) Verre de silice dopé au titandioxide et procédé de sa fabrication
EP1900694B1 (fr) Procédé de fabrication d'un substrat de verre de silice synthétique pour lasers excimères
US9278881B2 (en) EUV lithography member, making method, and titania-doped quartz glass
EP2684851B1 (fr) Verre de silice sythétique pour des moules de nanoimprint et procédé de fabrication du verre par hydrolyse à la flamme
JP5471478B2 (ja) エキシマレーザ用合成石英ガラスの製造方法
EP1754689B1 (fr) Substrat en verre de quartz synthétique pour laser excimére et procédé de fabrication
JP4831328B2 (ja) エキシマレーザ用合成石英ガラス基板の製造方法
JP5418428B2 (ja) 合成石英ガラスブロックの熱処理方法
JP4744046B2 (ja) 合成石英ガラス材料の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIC1 Information provided on ipc code assigned before grant

Ipc: C03C 4/00 20060101ALI20150701BHEP

Ipc: C03B 32/00 20060101ALI20150701BHEP

Ipc: C03C 3/06 20060101ALI20150701BHEP

Ipc: C03B 19/14 20060101AFI20150701BHEP

17P Request for examination filed

Effective date: 20160203

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17Q First examination report despatched

Effective date: 20170220

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170913

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 968710

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180215

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013032911

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 968710

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180507

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180607

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180507

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013032911

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20181108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180708

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180731

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180731

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130708

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180207

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20250529

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20250613

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250610

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250528

Year of fee payment: 13